Applied Surface Science 252 (2006) 8229–8234

www.elsevier.com/locate/apsusc

Electrical conductivity of chromate conversion coating on

electrodeposited zinc
Michal Tencer *
Nortel, Ottawa, Canada
Received 12 August 2005; received in revised form 23 August 2005; accepted 24 October 2005
Available online 28 November 2005

Abstract
For certain applications of galvanized steel protected with conversion coatings it is important that the surface is electrically conductive. This is
especially important with mating surfaces for electromagnetic compatibility. This paper addresses electrical conductivity of chromate conversion
coatings. A cross-matrix study using different zinc plating techniques by different labs showed that the main deciding factor is the type of zinc-
plating bath used rather than the subsequent chromating process. Thus, chromated zinc plate electrodeposited from cyanide baths is non-conductive
while that from alkaline (non-cyanide) and acid baths is conductive, even though the plate from all the bath types is conductive before conversion
coating. The results correlate well with the microscopic structure of the surfaces as observed with scanning electron microscopy (SEM) and could
be further corroborated and rationalized using EDX and Auger spectroscopies.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Chromate; Zinc plating; Conversion coating; Conductivity; EMI; EMC

1. Introduction Not surprisingly, electrical conductivity of conversion

A common practice of corrosion (‘‘red rust’’ formation)
protection of steel is to galvanize it with zinc. In turn, zinc itself
is protected from corroding (‘‘white rust’’ formation) by
chromate conversion coating. This type of coating is commonly
known as ‘‘zinc chromate’’ although the actual chemical
makeup of the surface is much more complex. The electrical
conductivity of chromate conversion coating is normally not a
concern. An important exception is when such materials are
used as mating surfaces for electromagnetic compatibility
where electrical contact to a ‘‘gasket’’ is needed to prevent
leakage of RF field known as electromagnetic interference
(EMI). The problem is limited to certain type of gaskets, e.g.,
fingerstock or conductive elastomer ones which cannot cut
through the conversion coating. Although the requirements for
the values of through resistance are not stringent (< 1 V for an
area of 1 cm2), not meeting it may result in non-conforming to
regulatory requirements for EMI.
* Present address: 21-F Banner Rd., Ottawa, ON, Canada K1Y 4H7. Tel.: +1
613 721 7186.
E-mail address: michaltencer@hotmail.com.
0169-4332/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2005.10.039
coatings is not a common area of study and it is hardly ever
mentioned. The purpose of this study is to gain insight into the
relationship between the electrical properties of the surface and
the galvanizing and conversion processes which may lead to the
excessive surface resistance. The scope is limited to the initial
properties and does not address the long term stability of the
chromate coating.
As far as industrial applications are concerned, the days of
chromate conversion coatings and other product containing
hexavalent chromium are counted, mostly because of the
European Union directive [1] banning CrVI with very few
exceptions and which, due to globalization of product lines is
expected o have consequences beyond EEC. However, one may
expect similar conductivity issues with alternative conversion
coating.
1.1. Zinc plating process
The main advantage of zinc plating of steel when compared
with nickel and other relatively inert metals is that it protects it
sacrificially from corrosion in case of the plate imperfections.
In fact, zinc is so electronegative (
0.76 V) that it could be
expected that it would not be electrodeposited from aqueous
8230 M. Tencer / Applied Surface Science 252 (2006) 8229–8234
solutions, gaseous hydrogen being formed instead. Only the
very high hydrogen overpotential on the substrate permits such
deposition. Accordingly, zinc cannot be deposited on graphite,
a material with low hydrogen overpotential and it is difficult to
plate zinc on cast iron which has graphite particles on the
surface [2].
In the plating process the plated part forms the cathode, a
basket filled with zinc balls is an anode and depending on the
geometry of the part additional steel anodes may be placed in
the bath as to improve the plating uniformity. This is related to
the current distribution. The initial ( primary) current
distribution is a function of the system geometry, but after a
short time the secondary current distribution is established.
This distribution depends additionally on the electrode
polarization (activation and concentration). Since the polar-
ization increases with current density, it acts as a factor
improving the current distribution as to form a more uniform
plate. The ability of a bath to plate uniformly geometrically
non-uniform parts is known as the throwing (or macrothrow-
ing) power. Depending on the type of coverage, Lowenheim [2]
lists the following types of microthrowing power: (a) negative
microthrow, (b) geometric levelling (conforming) and (c) true
levelling.
When the geometrical non-uniformities are very small, i.e.,
comparable with dimensions of the diffusion layer (i.e. the layer
whose thickness decides about the kinetics of ion diffusion
from the solution to the electrode), the considerations for the
throwing power do not hold anymore and we talk about
microthrowing or leveling power.
Smoothness on an even finer scale of surface topography
(smaller than the wavelength of the visible light) is related to
brightness, the ability of the surface to reflect light in a specular
rather than diffuse way. Brightness is mostly a function of the
size of deposited crystals (the smaller the brighter) and it is
usually controlled with the help of the so called brighteners,
bath additives which are adsorbed on the crystal surface and
control its growth rate. Brighteners are almost always
proprietary products.
The main difference between different zinc plating
processes is the type of the plating bath. There are many bath
types but we will limit our considerations to most common
ones, actually used in this study.
Cyanide baths are strongly alkaline solutions containing
cyanide ions. Both cyanide anions and hydroxyl anions can
complex zinc, thus the bath is a complex mixture containing,
among others, complex ions Zn(CN)4

, Zn(OH)4

,
Zn(OH)2(CN)2

, mixed complexes and uncomplexed
Zn++. Sodium is usually the counter-cation in these systems.
As the main deposited ions are negative, they have a
tendency to actually move away from the cathode (unlike in
the naive visualization of an electrolytic process), which
results in a large concentration polarization. This, in turn,
results in a good (macro)throwing power. On the other hand,
according to Lowenheim [2], the high concentration
polarization leads to a poor microthrowing (leveling) power.
As we will see later, the microthrowing power of the bath is
very important from the point of view of this project. Also,
according to Geduld [3], the deposits from cyanide baths are
characterized by relatively poor brightness when compared
with acid baths. Cyanide baths are well liked by platers
because of their throwing power and also because of the
relative stability of performance in function of the bath
composition, thus they are easy to control [3]. However, the
necessary process of destruction of the extremely toxic
cyanides in the process wastes before they can be discharged
is expensive and thus many platers prefer to use a different
types of plating bath.
Alkaline baths (non-cyanide) baths usually depend only on
hydroxyl ions to dissolve and complex zinc, thus zinc exists in
the solution mainly as Zn(OH)4

and Zn++. They are
characterized by a rather narrow optimum operating range of
chemical composition (especially the concentration of zinc)
and temperature and thus are difficult to control [3]. When
properly controlled, the alkaline bath can give a very bright
deposit. Generally, however, the brightness is more dependent
on addition of brighteners than with other baths. ‘‘Burning’’,
i.e. formation of a powdery amorphous black deposits is
sometimes a problem.
Acid (chloride) baths: In this type of bath zinc exists in the
form of zinc chloride i.e., the active species is Zn++. Some
proprietary formulations also contain ammonium salts or
chelating agents to complex zinc but the advantage of these
additives is uncertain [2]. Acids baths have the best leveling
ability (microthrowing power) and best brightness of all the
zinc plating baths [3]. Other advantages include energy savings
due to high conductivity of the bath and less hydrogen
embrittlement due to the high cathode efficiency (less hydrogen
evolution). From the plater’s point of view a most serious
drawback is the high corrosiveness of the acid bath requiring
special tank materials
1.2. Chromate conversion coatings
Immediately after zinc plating the parts are subjected to the
chromating process. For unpainted applications the corrosion
protections increases with coating thickness (measured as
coating weight) [4]. There are many proprietary chromate baths
but they all basically resemble the original 1936 Cronak process
from New Jersey Zinc [5] in which zinc was treated with a
solution of sodium dichromate in sulfuric acid [6,7]. The
chromate baths are strongly acidic and etching of the zinc
surface always accompanies and helps the chromating process.
In more acidic solutions the weigh loss due to zinc dissolution is
larger than the weight gain due to the coating formation. It is the
other way round in less acidic solutions and at a certain acidity
there is a zero net weight gain. Thus the estimation of the
coating thickness from the weight gain is rather uncertain. It is
assumed that the chromate coating thickness varies from 10 to
1000 nm (0.01 to 1 mm) [4]. The yellow coatings are usually
above 100 nm.
During the chromating process CrVI is reduced to CrIII while
zinc is oxidized to ZnII. Some of the products stay on the
surface, other diffuse away. Thus the composition of the surface
is very complex and is a function of the process and additives.
 M. Tencer / Applied Surface Science 252 (2006) 8229–8234 8231

Species encountered in the coating are Zn++, ZnO, CrO4

,

Cr2O3, SO4

and also a relatively large amount of water is
incorporated in the film. An X-ray photoelectron spectroscopy
study combined with depth profiling suggests [8] that CrVI
species are present close to the outer surface of the coating but
they quickly give way to CrIII as we enter the bulk of the
coating. Zn0 increases at the expense of ZnII (but much slower)
as we move in the same direction.
Freshly applied chromate films on zinc are soft and
gelatinous and can be easily scratched and abraded. The
coating ‘‘sets’’ over the next 24–48 h when it acquires its final
appearance. Even then a significant amount of water stays in the
coating. The presence of water seems to play an important role
in the corrosion protection. The protective properties of
chromate coatings are, indeed, destroyed upon heating above
70 8C. This has to be borne in mind when planning the
manufacturing cycle.
The resistivity of chromate films has only rarely been
considered. Geduld [7] quotes (without source) the following
values: clear chromate 1.5–7.5 mV/cm2, yellow chromate 15–
150 mV/cm2. Such values are clearly not reproducible. No Fig. 1. A constant force elastomeric conductivity probe, the basic idea.
other literature data were encountered.

2. Experimental general idea is shown in Fig. 1. The detailed description of the

2.1. Surface studies
Scanning electron microscopy (SEM) of surfaces was
performed with a field emission JEOL JSM-6300 F instrument.
Energy dispersive X-ray (EDX) spectra were obtained with
an attached to the above microscope LINK EXL probe.
Auger electron spectra (AES) were obtained with a Perkin-
Elmer physical electronics f 660 SAM instrument.
2.2. Resistance measurements
When measuring the through resistance of chromated
surfaces one has to make sure that the probe does not change
the structure of the chromate layer or cut through it to the
underlying metal. For this purpose two special conductivity
probes were designed and made in-house (Fig. 1). The probe’s
probe’s theory, design and operation will be published
elsewhere. The probes’ contact material is conductive silver
filled silicone rubber from Chomerics (an EMI gasket material).
A pre-stressed spring ensures that a constant force is acting on
the coating–probe interface and its value was adjusted to 1.0 kg
(10%).
The probes were connected to a multimeter so that two wire
resistance measurements were performed. The contact area of
the conductive eleastomer is 0.8 cm2 and all the conductivity
measurements relate to two probes, each with such area.
2.3. Platers and plating methods
Four plating suppliers (anonymous due to competitive
considerations) took part the cross-experiment study. They are
listed in table below with their techniques and materials used, if
revealed. Zinc plating steel from each supplier were chromated

Fig. 2. SEM pictures (4 kV, magnification 10,000) of chromated zinc plate originating from a cyanide baths: (a) zinc plated and chromated by Lab 1, (b) zinc plated
and chromated by Lab 3.
8232 M. Tencer / Applied Surface Science 252 (2006) 8229–8234

Table 1
Zinc plating and chromating baths used in the cross-experiment study
Laboratory Zinc plating bath Chromating bath
Supplier Type Supplier
#1 M.T. Harshaw GP45 Cyanide Enthon Endox 996
#2 Enthon 966 Alkaline Hansen and Wells Aquachrome 747
#3 M.T. Harshaw GP30 Cyanide M.T. Harshaw
M.T. Harshaw Acid
#4 Not revealed Alkaline Not revealed

in all of them for the study of conductivity and surface analysis. Table 2
All chromate coating studied were referred to as ‘‘yellow’’ Conductivity of zinc-chromated steel samples
(Table 1). Chromating by Lab Plating by Lab
#1 #2 #3 #4
3. Results and discussion
Cyanide Alkaline Acid Cyanide Alkaline

3.1. Conductivity of samples #1 (
) (+) (+) (
) (+)

#2 (
) (+) (+) (
) (+)
#3 (
) (+) (+) (
)
Surface resistance of chromated samples from the #4 () (+) (+) () (+)
participated laboratories was measured using two conduc-
The diagonal elements are for the plater’s own products. The non-diagonal
tivity probes described above and presented in Table 2. The
elements are results of the cross matrix experiment. (+) R < 1 V, (
) R > 1 kV,
measured through resistances spanned the whole measurable () R ffi 10 V.
range, from below 0.1 V, just below the probe sensitivity (the
ohmmeter/probes system has 0.3 V resistance) to open over time, being dependent on the age of the sample and,
circuit. There are no industry standards for the conductivity probably, the air humidity.
of chromated surfaces, therefore for this study, quite It is clear that the conductivity of the chromate conversion
arbitrarily, the following cutoff values were chosen: Samples coating is related to the zinc plating process rather than to the
whose resistance was uniformly across the surface in single subsequent chromating step. Irrespective of the further
V digits or better, i.e., < 10 V, was considered conductive treatment the samples originating with the cyanide zinc
and marked ‘‘(+)’’. In fact, those samples were almost always deposition were non-conductive.
below 1 V. Samples above this value as well as non-uniform On the other hand, before chromating, the all the zinc-plated
samples were considered non-conductive and marked ‘‘(
)’’. samples were conductive irrespective of the plating process
(The majority of these samples had resistance either in the (<0.1 V).
kV range or completely open.) A few borderline cases of bad The conductivity of the samples, which were both plated and
quality chromate (around 10 V) were given rating ‘‘()’’. It chromated in the same plant are given in Table 2 as the diagonal
is important to note here that with those samples which are elements of the plater matrix. These samples were much more
neither definitely conductive (i.e., well below 1 V) or numerous than the ones from the cross-experiment and
definitely non-conductive (open) the measured values of included also manufactured products. Thus they are more
conductivity were not stable and changed in both directions reliable from the statistical point of view.

Fig. 3. SEM pictures (4 kV, magnification 10,000) of chromated zinc plate originating from alkaline baths: (a) zinc plated and chromated by Lab 2, (b) zinc plated
by Lab 4, chromated by Lab 1.
 M. Tencer / Applied Surface Science 252 (2006) 8229–8234
Fig. 4. SEM picture (4 kV, magnification 10,000) of chromated zinc plate
originating from an acid bath, plated and chromated by Lab 3.
Further insights about the rationale of these facts were
gained through surface analysis.
3.2. Scanning electron microscopy
Examples of SEM pictures of chromated surfaces of samples
from the participating platers are shown in Figs. 2–4. At the
10,000 magnification with all the samples the chromate
coating is cracked [9] and the chromated surfaces have an
appearance of ‘‘clay soil during drought’’. Apparently, the
drying process of the conversion coating is accompanied by
cracking, not unlike with clay. The chromate conversion
coatings on aluminum has also been reported to have the same
type of appearance [10].
At the magnificationon used, i.e., on micron scale, the
samples from those platers who use alkaline non-cyanide
(Fig. 3) or acid process for zinc deposition (Fig. 4) appear flat
(smooth) and the distances between the cracks are large, on the
average 5–15 mm.
On the other hand, the samples originating from labs where
the cyanide bath is used for zinc deposition (Fig. 2) have a very
rich surface topography in the same scale of magnification.
There are ‘‘hills’’ and ‘‘valleys’’ about 0.3–1.5 mm in size
present on the surface. The chromate cracks follow the
Fig. 5. 12 kV EDX spectra of the chromated zinc plate of Fig. 2a. measured (a) on top of a hill, (b) in a valley.
8233
‘‘valleys’’ so that the average distance between the cracks is
only about 1 mm.
These features are correlated with the conductivity of the
surface.
3.3. X-ray spectroscopy (EDX)
The initial purpose of this study was to detect the presence of
any contaminants (possibly organic) on chromated surfaces as
contamination was one of suspected reasons of the low electrical
conductivity. However, besides traces of carbon present on all
surfaces exposed to air no significant contamination was detected
in any of the samples, in other words no other elements than those
expected from the composition of baths were present. The EDX
spectra of a ‘‘cyanide’’ zinc/chromated sample are shown in
Fig. 5. The 12 kV spectrum shown in Fig. 5a, which was taken
from the top of a ‘‘hill’’ (compare with the SEM picture, Fig. 2a)
shows the expected presence of chromium, oxygen and zinc. The
12 kV spectrum taken from a crack in the chromate coating
(Fig. 5b) shows additionally the presence of iron, which would
indicate that the cracks are deep and extend into zinc itself. It is
also interesting to notice that the relative ratio of chromium to
zinc is much higher in the crack than on the hill. This can be
explained if the structure of the coating approximates the one
shown in Fig. 6.
A structure like the one in Fig. 2 would be formed when the
zinc coating has ‘‘porous’’ structure due to a poor, possibly
negative microthrowing power. Indeed, as mentioned above,
cyanide baths are known to have poor leveling power. It was
therefore interesting to see the surface of the zinc plate from a
cyanide bath before chromating. A SEM picture (magnification
10,000) of such zinc plated sample is shown in Fig. 7. We can
see that the surface topography is rich, but somewhat less so
than that of the chromated sample. Apparently, etching
accompanying the chromating process accentuates the ‘‘por-
osity’’ of the surface.
3.4. Auger electron spectroscopy (AES)
The surface character presented in Fig. 2 has been further
corroborated by a Auger electron spectrum of a ‘‘cyanide’’ zinc
8234 M. Tencer / Applied Surface Science 252 (2006) 8229–8234
Fig. 6. Structure of zinc galvanized steel from the cyanide process with chromate conversion coating as deduced from SEM, EDX and AES.
Fig. 7. SEM picture (4 kV, magnification 10,000) of zinc plate originating
from a cyanide bath (same as in Fig. 2a), before chromating.
chromated sample (Fig. A9). This spectrum was taken from a
‘‘hill’’ location. Since the penetration depth of Auger electrons
is very small, we have here a genuine surface spectrum.
Accordingly, chromium and oxygen are the only elements
observed. Unfortunately, chromium is one of those elements for
which it is difficult to distinguish oxidation states using AES.
No zinc or iron were observed and no organic contamination
was detected, even within the extremely thin top layer of
chromate which is not more than 10–15 atoms thick. This
further corroborates the structure proposed in Fig. 6.
3.5. Abrasive post treatments
Faced with the conversion coating conductivity issue, some
collaborating platers proposed abrasive post treatment (e.g.,
with a pencil eraser or a household green scrubby). The
treatment does neither change the general surface structure nor
removes any significant amount of material. The only effect
seems to be the formation of grooves in the coating. A soft
conductivity probe (silicone rubber) used in this study can
conform to these grooves, which extend into the conductive
zinc-chromate and renders the apparent reading ‘‘conductive’’.
However, in terms of the mating contact for electromagnetic
compatibility, a non-compliant finger type gasket would not
reach the conductive areas and the EMC performance would
not benefit from this treatment. The pencil eraser treatment
seems, on the other hand, result in considerably thinning of the
chromate layer.
Acknowledgments
The author would like to thank Mr. Gerry Smith for his
excellent technical help with scanning electron microscopy and
surface spectroscopy and to Dr. John Moss for the original idea
of the constant force conductivity probe.
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